CN110790973A - Plastic particle for recycling water surface oil stains - Google Patents
Plastic particle for recycling water surface oil stains Download PDFInfo
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- CN110790973A CN110790973A CN201911014867.1A CN201911014867A CN110790973A CN 110790973 A CN110790973 A CN 110790973A CN 201911014867 A CN201911014867 A CN 201911014867A CN 110790973 A CN110790973 A CN 110790973A
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Abstract
The invention discloses plastic particles for water surface oil stain recovery treatment, which are prepared by the following steps: 1) adding microcrystalline cellulose into sulfuric acid, and reacting to obtain a nano cellulose suspension; 2) adding epoxy chloropropane into the nano cellulose suspension to prepare cellulose aerogel; 3) preparing methacrylic acid fluorine-containing copolymer by adopting butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide; 4) modifying the cellulose aerogel to obtain modified cellulose aerogel; 5) the modified cellulose aerogel powder with talcum powder as a carrier, waste plastics, a catalyst and a foaming agent are subjected to a double-screw extruder to obtain plastic particles. The plastic particles have the hydrophobic-oleophilic/oleophobic-hydrophilic conversion function along with the difference of water environments, can adsorb oil stains in water and purify water, and the adsorbed oil stains are easy to discharge, so that the plastic particles have reusability and wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to plastic particles for water surface oil stain recovery treatment.
Background
At present, the oil spill and leakage problems caused by increasingly frequent offshore oil exploitation activities and offshore transportation have serious influence on the ecological environment and human health, and the total amount of oil pollutants entering the ocean through rivers or offshore accidents all over the world is reported to reach more than 10Mt every year, so that the ecological environment and the marine biosphere of the ocean are seriously influenced and polluted. The petroleum pollutants floating on large-area water body are difficult to be removed by common chemical or physical methods, and meanwhile, the petroleum pollutants are gradually oxidized under the action of strong illumination to generate a tan jelly substance which comprises some toxic phenolic chemical substances, so that more serious secondary chemical substance pollution is caused. Therefore, effective control of oil slick spreading and cleaning has become one of the international challenges to be solved.
At present, the main treatment measures of offshore oil spill comprise a physical method, a biological method and a chemical method. The three methods are different in use condition and complement each other, wherein the oil condensing agent in the chemical method is widely concerned by scientific researchers and even the industry because of the advantages of high oil condensing speed, small secondary pollution and the like. The oil gelling agent is a chemical treatment agent which can gel the sleep oil spill to form a thick semisolid or solid block which can float on the water surface. Various oil-condensing agents such as amino acids, sorbitols, proteins, starches and the like are synthesized at home and abroad in the last 60 to 90 years, but the materials have the problems of low oil-condensing efficiency, high cost and the like, and currently, the requirements of practical application cannot be met.
Therefore, how to improve the treatment efficiency and the treatment cost of offshore oil pollution is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the existing problems and provides plastic particles for recycling and treating oil stains on water surfaces.
The invention is realized by the following technical scheme:
a plastic particle for recycling water surface oil stains is specifically prepared by the following steps:
1) adding microcrystalline cellulose into a sulfuric acid solution, heating to 40-50 ℃, stirring for reaction for 2-3h, then adding pure water in an amount which is 10-13 times that of the sulfuric acid solution to stop the reaction, washing and centrifugally separating the product for 4-5 times by using the pure water, dialyzing the obtained precipitate in the pure water for 5-7d until the water solution is neutral, adding the dialyzed precipitate into the pure water, and oscillating and dispersing to obtain a nano cellulose suspension;
2) adding epoxy chloropropane into the nano-cellulose suspension, pouring the mixed solution into a mould, placing the mould in an oven at 60-70 ℃ for reaction for 30-40min to obtain cellulose hydrogel, washing the cellulose hydrogel with deionized water to remove impurities until the cellulose hydrogel is neutral, and then freeze-drying the cellulose hydrogel at-55 to-65 ℃ for 30-40h to obtain cellulose aerogel;
3) under the protection of nitrogen, sequentially adding butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide into a reactor, heating to 70-80 ℃, reacting at a constant temperature for 7-10h, putting a reaction product into an ethanol solution for precipitation, dissolving the ethanol precipitate for multiple times by using tetrahydrofuran, then putting the product into a vacuum oven, and drying at 45-55 ℃ for 5-8h to obtain the methacrylic acid fluorine-containing copolymer;
4) placing cellulose aerogel, cuprous bromide and methacrylic acid fluorine-containing copolymer in a reactor, filling nitrogen to remove oxygen in the reactor, adding a mixed solution of dehydrated tetrahydrofuran, isopropanol and 2-vinylpyridine, adding pentamethyldiethylenetriamine, heating to 60-70 ℃, stirring at the rotating speed of 70-100r/min for reaction for 20-25h, washing a product with ethanol, and performing vacuum drying at the temperature of 40-50 ℃ for 10-15h to obtain modified cellulose aerogel;
5) adding modified cellulose aerogel into a methanol solution, mixing and stirring to prepare a modified cellulose aerogel methanol dispersion solution, then adding talcum powder, oscillating and dispersing for 20-30min under 300-plus-500W ultrasonic wave, then performing centrifugal separation, washing, drying and airflow crushing to obtain modified cellulose aerogel powder taking the talcum powder as a carrier, and then mixing the powder with cleaned waste plastic, a catalyst and a foaming agent according to the proportion of 5-9%: 80-87%: 4-6%: 3 to 5 percent of the weight percent of the mixture is evenly mixed, and the plastic particles can be prepared by a double-screw extruder.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 1), the mass fraction of the sulfuric acid solution is 63-70%; the mass volume ratio of the microcrystalline cellulose to the sulfuric acid solution is 1:10-15 g/ml; the concentration of the nano-cellulose suspension is 1-1.5 g/ml; the rotating speed of the stirring reaction is 50-80 r/min.
Preferably, the plastic particles are used for the oil stain recovery treatment of the water surface, wherein in the step 2), the volume ratio of the epichlorohydrin to the nano-cellulose suspension is 1: 9-12.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 3), the mass ratio of the butyl methacrylate to the fluorooctyl ethyl methacrylate to the toluene to the benzoyl peroxide is 7-10:5-8:40-50: 0.2-0.5; the mass volume ratio of the reaction product to the ethanol solution is 1:30-40g/ml, and the mass fraction of the ethanol is 65-80%; the volume ratio of the tetrahydrofuran to the ethanol solution is 1: 15-20.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 4), the mass ratio of the cellulose aerogel, cuprous bromide, methacrylic acid fluorine-containing copolymer and the mixed solution is 2-4:1:6-8: 20-30; the mass volume ratio of tetrahydrofuran, isopropanol and 2-vinylpyridine in the mixed solution is 13-17 ml: 4-6 ml: 1g of a compound; the mass ratio of the addition amount of the pentamethyl diethylenetriamine to the cellulose aerogel is 1: 2-2.5.
Preferably, the plastic particles are used for the recovery treatment of the oil stain on the water surface, wherein in the step 5), the preparation method of the catalyst comprises the following steps: adding 10-15 parts of acetonitrile into a reactor, adding 2-3 parts of cerium trichloride and 1-2 parts of sodium iodide, stirring and mixing uniformly at the rotation speed of 150-200r/min, slowly adding 0.5-0.8 part of silica gel under the stirring state, continuously stirring for 20-30h at room temperature, then recovering the acetonitrile in the system by using a rotary evaporator, and drying the product for 6-8h at the temperature of 50-60 ℃.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 5), the mass fraction of the modified cellulose aerogel in the modified cellulose aerogel methanol dispersion liquid is 5-8%; the mass volume ratio of the talcum powder to the modified cellulose aerogel methanol dispersion liquid is 1:10-20 g/ml; the particle size of the modified cellulose aerogel powder taking the talcum powder as the carrier is 5-10 um; the foaming agent is any one of azo compounds, sulfonyl hydrazine compounds and nitroso compounds; the melting temperature of the double-screw extruder is 175-185 ℃; the waste plastic is at least one of recovered waste ABS plastic, waste PC plastic, waste PE plastic and waste HDPE plastic.
Preferably, the plastic particles are used for the recovery treatment of the oil stain on the water surface, wherein the use method of the plastic particles comprises the following steps: putting plastic particles on a water surface polluted by oil stains, after the oil stains on the water surface are removed completely, recycling the plastic particles, putting the plastic particles into water containing hydrogen peroxide, adding a proper amount of nano zinc oxide, treating for 3-4h under 500-plus-600W microwave radiation, taking out the plastic particles, naturally airing, and then performing heat treatment for 3-4h in an oven at 60-70 ℃, wherein the content of the hydrogen peroxide in the water is 0.3-0.8%, and the adding amount of the nano zinc oxide is 1-2% of the total weight of the water body; according to the application, plastic particles adsorbing oil stains are placed in water to be subjected to microwave radiation treatment, when the plastic particles are in contact with an aqueous medium, a catalyst contained in the plastic particles can promote rearrangement of different groups in the modified cellulose aerogel under the action of microwave radiation, hydrophilic hydroxyl groups in the modified cellulose aerogel can be directionally arranged on an interface between the modified cellulose aerogel and the water along with the prolonging of the contact time with the water, a strong hydrogen bond is formed with the water on the interface, hydrophobic fluorine-containing groups are arranged loosely on the interface and gradually migrate to an inner layer of the interface, so that the surface performance of the modified cellulose aerogel is hydrophilic-oleophobic, and the oil stains in the plastic particles can be gradually discharged along with the water absorption of the modified cellulose aerogel, so that the oil stains can be recovered; by adding hydrogen peroxide into water, under the combined action of a nano zinc oxide catalyst and microwaves, hydroxyl radicals can be generated, the generated hydroxyl radicals can be attached to the surface of the modified cellulose aerogel, so that the hydroxyl content of the surface of the modified cellulose aerogel is increased, the conversion of the surface energy of the modified cellulose aerogel can be promoted, and the discharge of oil stains in plastics is promoted; through carrying out heat treatment after the plastic particles are dried in the air, due to the contact with the air, in order to enable the modified cellulose aerogel in the plastic particles to have the lowest surface tension, under the action of thermodynamic driving force, hydrophobic-lipophilic fluorine-containing groups are gathered on the interface between the modified cellulose aerogel and the air, and hydrophilic hydroxyl groups are located in the inner layer of the interface, so that hydrophilic groups are blocked by hydrophobic groups, the surface of the modified cellulose aerogel is hydrophobic, and the plastic can be repeatedly used.
Compared with the prior art, the invention has the following advantages:
according to the invention, through graft polymerization reaction, fluorine-containing groups are introduced to the surface of the cellulose aerogel with a porous structure, and the cellulose aerogel is directionally arranged on the outer surface of the cellulose aerogel, so that the modified cellulose aerogel with hydrophobicity-lipophilicity is prepared, then talcum powder is used as a carrier, the modified cellulose aerogel is adsorbed on pores and the surface, so that modified cellulose aerogel powder with the talcum powder as the carrier is obtained, and then the modified cellulose aerogel powder is prepared by mixing the powder with plastic, a catalyst and a foaming agent and then passing through a double-screw extruder; the plastic particles have the hydrophobic-oleophilic/oleophobic-hydrophilic conversion function along with different water body environments, so that oil stains in the water body can be effectively adsorbed, the water quality is purified, the adsorbed oil stains can be discharged, the plastic particles have reusability, the discharged oil stains can be recycled, and natural resources can be effectively saved; the added catalyst can promote the conversion of the surface performance of the modified cellulose aerogel under the action of microwave radiation; the added foaming agent can make the prepared plastic particles have a microporous structure and can provide a flow channel for water and oil stains; the added talcum powder can improve the performance of the plastic particles, and can provide a storage space for the adsorbed oil stains, so that the oil absorption performance of the plastic particles can be improved.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
A plastic particle for recycling water surface oil stains is specifically prepared by the following steps:
1) adding microcrystalline cellulose into a sulfuric acid solution, heating to 40 ℃, stirring for reaction for 3 hours, then adding pure water 10 times of the sulfuric acid solution to stop the reaction, washing and centrifugally separating the product for 4 times by using the pure water, dialyzing the obtained precipitate in the pure water for 5 days until the water solution is neutral, adding the dialyzed precipitate into the pure water, and oscillating and dispersing to obtain a nano cellulose suspension;
2) adding epoxy chloropropane into the nano-cellulose suspension, pouring the mixed solution into a mould, placing the mould in an oven at 60 ℃ for reaction for 40min to obtain cellulose hydrogel, washing the cellulose hydrogel with deionized water to remove impurities until the cellulose hydrogel is neutral, and then freezing and drying the cellulose hydrogel at-55 ℃ for 40h to obtain cellulose aerogel;
3) under the protection of nitrogen, sequentially adding butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide into a reactor, heating to 70 ℃, reacting at a constant temperature for 10 hours, putting a reaction product into an ethanol solution for precipitation, dissolving the ethanol precipitate for multiple times by using tetrahydrofuran, then putting the product into a vacuum oven, and drying at 45 ℃ for 8 hours to obtain the methacrylic acid fluorine-containing copolymer;
4) placing cellulose aerogel, cuprous bromide and methacrylic acid fluorine-containing copolymer in a reactor, introducing nitrogen to remove oxygen in the reactor, adding a mixed solution of dehydrated tetrahydrofuran, isopropanol and 2-vinylpyridine, adding pentamethyldiethylenetriamine, heating to 60 ℃, stirring at the rotating speed of 70r/min for reaction for 25h, washing a product with ethanol, and performing vacuum drying at the temperature of 40 ℃ for 15h to obtain the modified cellulose aerogel;
5) adding modified cellulose aerogel into a methanol solution, mixing and stirring to prepare a modified cellulose aerogel methanol dispersion solution, then adding talcum powder, oscillating and dispersing for 30min under 300W ultrasonic wave, then performing centrifugal separation, washing, drying and airflow crushing to obtain modified cellulose aerogel powder taking the talcum powder as a carrier, and then mixing the powder with cleaned waste plastic, a catalyst and a foaming agent according to the proportion of 5%: 87%: 5%: 3 percent of the weight percentage are evenly mixed, and the plastic particles can be prepared by a double-screw extruder.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 1), the mass fraction of the sulfuric acid solution is 63%; the mass volume ratio of the microcrystalline cellulose to the sulfuric acid solution is 1:10 g/ml; the concentration of the nano-cellulose suspension is 1 g/ml; the rotating speed of the stirring reaction is 50 r/min.
Preferably, the plastic particles are used for the oil stain recovery treatment of the water surface, wherein in the step 2), the volume ratio of the epichlorohydrin to the nano-cellulose suspension is 1: 9.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 3), the mass ratio of butyl methacrylate to fluorooctyl ethyl methacrylate to toluene to benzoyl peroxide is 7:5:40: 0.2; the mass volume ratio of the reaction product to the ethanol solution is 1:30g/ml, and the mass fraction of the ethanol is 65%; the volume ratio of the tetrahydrofuran to the ethanol solution is 1: 15.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 4), the mass ratio of the cellulose aerogel, cuprous bromide, methacrylic acid fluorine-containing copolymer and the mixed solution is 2:1:6: 20; the mass volume ratio of tetrahydrofuran, isopropanol and 2-vinylpyridine in the mixed solution is 13 ml: 4 ml: 1g of a compound; the mass ratio of the addition amount of the pentamethyl diethylenetriamine to the cellulose aerogel is 1:2.
Preferably, the plastic particles are used for the recovery treatment of the oil stain on the water surface, wherein in the step 5), the preparation method of the catalyst comprises the following steps: adding 10 parts of acetonitrile into a reactor, adding 2 parts of cerium trichloride and 1 part of sodium iodide, stirring and mixing uniformly at the rotating speed of 150r/min, slowly adding 0.5 part of silica gel under the stirring state, continuously stirring at room temperature for 30h, then recovering the acetonitrile in the system by using a rotary evaporator, and drying the product at 50 ℃ for 8 h.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 5), the mass fraction of the modified cellulose aerogel in the modified cellulose aerogel methanol dispersion liquid is 5%; the mass volume ratio of the talcum powder to the modified cellulose aerogel methanol dispersion liquid is 1:10 g/ml; the particle size of the modified cellulose aerogel powder taking the talcum powder as the carrier is 5 um; the foaming agent is any one of azo compounds, sulfonyl hydrazine compounds and nitroso compounds; the melting temperature of the twin-screw extruder is 175 ℃; the waste plastic is at least one of recovered waste ABS plastic, waste PC plastic, waste PE plastic and waste HDPE plastic.
Preferably, the plastic particles for the recovery treatment of the oil stain on the water surface are used by the following method: putting plastic particles on a water surface polluted by oil stains, after the oil stains on the water surface are removed completely, recycling the plastic particles, putting the plastic particles into water containing hydrogen peroxide, adding a proper amount of nano zinc oxide, treating for 4 hours under 500W microwave radiation, taking out the plastic particles, naturally drying, and then performing heat treatment for 4 hours in a 60 ℃ oven, wherein the content of the hydrogen peroxide in the water is 0.3%, and the addition amount of the nano zinc oxide is 1% of the total weight of the water body.
Example 2
A plastic particle for recycling water surface oil stains is specifically prepared by the following steps:
1) adding microcrystalline cellulose into a sulfuric acid solution, heating to 45 ℃, stirring for reaction for 2.5 hours, then adding pure water 11 times of the sulfuric acid solution to stop the reaction, washing and centrifugally separating the product for 4 times by using the pure water, dialyzing the obtained precipitate in the pure water for 6 days until the aqueous solution is neutral, adding the dialyzed precipitate into the pure water, and oscillating and dispersing to obtain a nano cellulose suspension;
2) adding epoxy chloropropane into the nano-cellulose suspension, pouring the mixed solution into a mould, placing the mould in a 65 ℃ oven for reaction for 35min to obtain cellulose hydrogel, washing the cellulose hydrogel with deionized water to remove impurities until the cellulose hydrogel is neutral, and then freezing and drying the cellulose hydrogel at-60 ℃ for 35h to obtain cellulose aerogel;
3) under the protection of nitrogen, sequentially adding butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide into a reactor, heating to 75 ℃, reacting at a constant temperature for 8 hours, putting a reaction product into an ethanol solution for precipitation, dissolving the ethanol precipitate for multiple times by using tetrahydrofuran, then putting the product into a vacuum oven, and drying at 50 ℃ for 7 hours to obtain the methacrylic acid fluorine-containing copolymer;
4) placing cellulose aerogel, cuprous bromide and methacrylic acid fluorine-containing copolymer in a reactor, introducing nitrogen to remove oxygen in the reactor, adding a mixed solution of dehydrated tetrahydrofuran, isopropanol and 2-vinylpyridine, adding pentamethyldiethylenetriamine, heating to 65 ℃, stirring and reacting at the rotating speed of 85r/min for 23h, washing a product with ethanol, and performing vacuum drying at the temperature of 45 ℃ for 12h to obtain the modified cellulose aerogel;
5) adding modified cellulose aerogel into a methanol solution, mixing and stirring to prepare a modified cellulose aerogel methanol dispersion solution, then adding talcum powder, oscillating and dispersing for 25min under 400W ultrasonic wave, then performing centrifugal separation, washing, drying and airflow crushing to obtain modified cellulose aerogel powder taking the talcum powder as a carrier, and then mixing the powder with cleaned waste plastic, a catalyst and a foaming agent according to the proportion of 8%: 82%: 6%: 4 percent of the weight percentage are evenly mixed, and the plastic particles can be prepared by a double-screw extruder.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 1), the mass fraction of the sulfuric acid solution is 67%; the mass volume ratio of the microcrystalline cellulose to the sulfuric acid solution is 1:12 g/ml; the concentration of the nano-cellulose suspension is 1.3 g/ml; the rotating speed of the stirring reaction is 70 r/min.
Preferably, the plastic particles are used for the oil stain recovery treatment of the water surface, wherein in the step 2), the volume ratio of the epichlorohydrin to the nano-cellulose suspension is 1: 10.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 3), the mass ratio of butyl methacrylate to fluorooctyl ethyl methacrylate to toluene to benzoyl peroxide is 8:7:45: 0.3; the mass volume ratio of the reaction product to the ethanol solution is 1:35g/ml, and the mass fraction of the ethanol is 75%; the volume ratio of the tetrahydrofuran to the ethanol solution is 1: 18.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 4), the mass ratio of the cellulose aerogel, cuprous bromide, methacrylic acid fluorine-containing copolymer and the mixed solution is 3:1:7: 25; the mass volume ratio of tetrahydrofuran, isopropanol and 2-vinylpyridine in the mixed solution is 15 ml: 5 ml: 1g of a compound; the mass ratio of the addition amount of the pentamethyl diethylenetriamine to the cellulose aerogel is 1: 2.3.
Preferably, the plastic particles are used for the recovery treatment of the oil stain on the water surface, wherein in the step 5), the preparation method of the catalyst comprises the following steps: adding 12 parts of acetonitrile into a reactor, adding 2.5 parts of cerium trichloride and 1.5 parts of sodium iodide, stirring and mixing uniformly at the rotation speed of 170r/min, slowly adding 0.7 part of silica gel under the stirring state, continuously stirring at room temperature for 25 hours, then recovering the acetonitrile in the system by using a rotary evaporator, and drying the product at 55 ℃ for 7 hours.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 5), the mass fraction of the modified cellulose aerogel in the modified cellulose aerogel methanol dispersion liquid is 7%; the mass volume ratio of the talcum powder to the modified cellulose aerogel methanol dispersion liquid is 1:15 g/ml; the particle size of the modified cellulose aerogel powder taking the talcum powder as the carrier is 8 um; the foaming agent is any one of azo compounds, sulfonyl hydrazine compounds and nitroso compounds; the melting temperature of the double-screw extruder is 180 ℃; the waste plastic is at least one of recovered waste ABS plastic, waste PC plastic, waste PE plastic and waste HDPE plastic.
Preferably, the plastic particles for the recovery treatment of the oil stain on the water surface are used by the following method: putting plastic particles on a water surface polluted by oil stains, after the oil stains on the water surface are cleaned, recycling the plastic particles, putting the plastic particles into water containing hydrogen peroxide, adding a proper amount of nano zinc oxide, treating for 3.5 hours under 550W microwave radiation, taking out the plastic particles, naturally drying, and then carrying out heat treatment for 3.5 hours in a 65 ℃ drying oven, wherein the content of the hydrogen peroxide in the water is 0.5%, and the addition amount of the nano zinc oxide is 1.5% of the total weight of the water body.
Example 3
A plastic particle for recycling water surface oil stains is specifically prepared by the following steps:
1) adding microcrystalline cellulose into a sulfuric acid solution, heating to 50 ℃, stirring for reaction for 2 hours, then adding pure water 13 times the amount of the sulfuric acid solution to stop the reaction, washing and centrifugally separating the product for 5 times by using the pure water, dialyzing the obtained precipitate in the pure water for 7 days until the water solution is neutral, adding the dialyzed precipitate into the pure water, and oscillating and dispersing to obtain a nano cellulose suspension;
2) adding epoxy chloropropane into the nano-cellulose suspension, pouring the mixed solution into a mould, placing the mould in an oven at 70 ℃ for reaction for 30min to obtain cellulose hydrogel, washing the cellulose hydrogel with deionized water to remove impurities until the cellulose hydrogel is neutral, and then freeze-drying the cellulose hydrogel at-65 ℃ for 30h to obtain cellulose aerogel;
3) under the protection of nitrogen, sequentially adding butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide into a reactor, heating to 70 ℃, reacting at a constant temperature for 10 hours, putting a reaction product into an ethanol solution for precipitation, dissolving the ethanol precipitate for multiple times by using tetrahydrofuran, then putting the product into a vacuum oven, and drying at 45 ℃ for 8 hours to obtain the methacrylic acid fluorine-containing copolymer;
4) placing cellulose aerogel, cuprous bromide and methacrylic acid fluorine-containing copolymer in a reactor, introducing nitrogen to remove oxygen in the reactor, adding a mixed solution of dehydrated tetrahydrofuran, isopropanol and 2-vinylpyridine, adding pentamethyldiethylenetriamine, heating to 70 ℃, stirring and reacting at the rotating speed of 100r/min for 20 hours, washing a product with ethanol, and performing vacuum drying at the temperature of 50 ℃ for 10 hours to obtain modified cellulose aerogel;
5) adding modified cellulose aerogel into a methanol solution, mixing and stirring to prepare a modified cellulose aerogel methanol dispersion solution, then adding talcum powder, oscillating and dispersing for 20min under 500W ultrasonic wave, then performing centrifugal separation, washing, drying and airflow crushing to obtain modified cellulose aerogel powder taking the talcum powder as a carrier, and then mixing the powder with cleaned waste plastic, a catalyst and a foaming agent according to the proportion of 9%: 80%: 6%: 5 percent of the components are uniformly mixed, and the plastic particles can be prepared by a double-screw extruder.
Preferably, the plastic particles are used for recycling and treating oil stains on water surfaces, wherein in the step 1), the mass fraction of the sulfuric acid solution is 70%; the mass volume ratio of the microcrystalline cellulose to the sulfuric acid solution is 1:15 g/ml; the concentration of the nano-cellulose suspension is 1.5 g/ml; the rotating speed of the stirring reaction is 80 r/min.
Preferably, the plastic particles are used for the oil stain recovery treatment of the water surface, wherein in the step 2), the volume ratio of the epichlorohydrin to the nano-cellulose suspension is 1: 12.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 3), the mass ratio of butyl methacrylate to fluorooctyl ethyl methacrylate to toluene to benzoyl peroxide is 10:8:50: 0.5; the mass volume ratio of the reaction product to the ethanol solution is 1:40g/ml, and the mass fraction of the ethanol is 80%; the volume ratio of the tetrahydrofuran to the ethanol solution is 1: 20.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 4), the mass ratio of the cellulose aerogel, cuprous bromide, methacrylic acid fluorine-containing copolymer and the mixed solution is 4:1:8: 30; the mass volume ratio of tetrahydrofuran, isopropanol and 2-vinylpyridine in the mixed solution is 17 ml: 6 ml: 1g of a compound; the mass ratio of the addition amount of the pentamethyl diethylenetriamine to the cellulose aerogel is 1: 2.5.
Preferably, the plastic particles are used for the recovery treatment of the oil stain on the water surface, wherein in the step 5), the preparation method of the catalyst comprises the following steps: adding 15 parts of acetonitrile into a reactor, adding 3 parts of cerium trichloride and 2 parts of sodium iodide, stirring and mixing uniformly at the rotating speed of 200r/min, slowly adding 0.8 part of silica gel under the stirring state, continuously stirring at room temperature for 20 hours, then recovering the acetonitrile in the system by using a rotary evaporator, and drying the product at 60 ℃ for 6 hours.
Preferably, the plastic particles are used for water surface oil stain recovery treatment, wherein in the step 5), the mass fraction of the modified cellulose aerogel in the modified cellulose aerogel methanol dispersion liquid is 8%; the mass volume ratio of the talcum powder to the modified cellulose aerogel methanol dispersion liquid is 1:20 g/ml; the particle size of the modified cellulose aerogel powder taking the talcum powder as the carrier is 10 um; the foaming agent is any one of azo compounds, sulfonyl hydrazine compounds and nitroso compounds; the melting temperature of the twin-screw extruder is 185 ℃; the waste plastic is at least one of recovered waste ABS plastic, waste PC plastic, waste PE plastic and waste HDPE plastic.
Preferably, the plastic particles for the recovery treatment of the oil stain on the water surface are used by the following method: putting plastic particles on a water surface polluted by oil stains, after the oil stains on the water surface are removed completely, recycling the plastic particles, putting the plastic particles into water containing hydrogen peroxide, adding a proper amount of nano zinc oxide, treating for 3 hours under 600W microwave radiation, taking out the plastic particles, naturally drying, and then performing heat treatment for 3 hours in a 70 ℃ oven, wherein the content of the hydrogen peroxide in the water is 0.8%, and the addition amount of the nano zinc oxide is 2% of the total weight of the water body.
Test example 1: the oil absorption performance of the plastic granules of examples 1-3 was tested separately by the following method: using kerosene as a test oil product, putting plastic particles into a 1L beaker containing enough kerosene for absorption, standing for 4h, wiping off the kerosene on the surface of the plastic particles by using filter paper, and weighing, wherein the calculation formula of the oil absorption multiplying power is as follows: oil absorption multiplying power A = (W1-W0)/W0, wherein A is the oil absorption multiplying power of the plastic particles, W1 is the mass of the plastic particles after oil absorption, and W0 is the mass of the dried plastic particles before oil absorption;
test example 2: the using methods provided in examples 1-3 were respectively used to treat the oil-absorbed plastic particles, and the oil recovery rate of the plastic microspheres was tested, with the calculation formula for the oil recovery rate being: the oil recovery rate S = (W3-W2)/(W1-W0). times.100%, wherein W3 is the total mass of oil discharged from the beaker and the plastic particles, W2 is the mass of the beaker before the plastic particles are placed, W1 is the mass of the plastic particles after oil absorption, and W0 is the mass of the dried plastic particles before oil absorption;
test example 3: the plastic particles in the test example 2 are subjected to secondary oil absorption performance and oil recovery rate tests according to the methods of the test example 1 and the test example 2 respectively, and the oil absorption multiplying power and the oil recovery rate of the secondary use of the plastic particles are calculated;
the results of the above tests are shown in the following table:
| is used for one time | Example 1 | Example 2 | Example 3 |
| Oil absorption multiplying power g/g | 21.5 | 23.2 | 22.6 |
| Oil recovery rate% | 82.6 | 84.1 | 83.2 |
| For the second use | Example 1 | Example 2 | Example 3 |
| Oil absorption multiplying power g/g | 21.3 | 23.0 | 22.4 |
| Oil recovery rate% | 82.2 | 83.7 | 82.9 |
As can be seen from the above table, the plastic particles provided by the invention have excellent oil absorption multiplying power, can effectively absorb oil stains in water, and the absorbed oil stains are easy to discharge and high in recovery rate, and meanwhile, the plastic particles have reusability and the performance is still well maintained.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (8)
1. The plastic particles for recycling the oil stains on the water surface are characterized by comprising the following specific preparation methods:
1) adding microcrystalline cellulose into a sulfuric acid solution, heating to 40-50 ℃, stirring for reaction for 2-3h, then adding pure water in an amount which is 10-13 times that of the sulfuric acid solution to stop the reaction, washing and centrifugally separating the product for 4-5 times by using the pure water, dialyzing the obtained precipitate in the pure water for 5-7d until the water solution is neutral, adding the dialyzed precipitate into the pure water, and oscillating and dispersing to obtain a nano cellulose suspension;
2) adding epoxy chloropropane into the nano-cellulose suspension, pouring the mixed solution into a mould, placing the mould in an oven at 60-70 ℃ for reaction for 30-40min to obtain cellulose hydrogel, washing the cellulose hydrogel with deionized water to remove impurities until the cellulose hydrogel is neutral, and then freeze-drying the cellulose hydrogel at-55 to-65 ℃ for 30-40h to obtain cellulose aerogel;
3) under the protection of nitrogen, sequentially adding butyl methacrylate, fluorooctyl ethyl methacrylate, toluene and benzoyl peroxide into a reactor, heating to 70-80 ℃, reacting at a constant temperature for 7-10h, putting a reaction product into an ethanol solution for precipitation, dissolving the ethanol precipitate for multiple times by using tetrahydrofuran, then putting the product into a vacuum oven, and drying at 45-55 ℃ for 5-8h to obtain the methacrylic acid fluorine-containing copolymer;
4) placing cellulose aerogel, cuprous bromide and methacrylic acid fluorine-containing copolymer in a reactor, filling nitrogen to remove oxygen in the reactor, adding a mixed solution of dehydrated tetrahydrofuran, isopropanol and 2-vinylpyridine, adding pentamethyldiethylenetriamine, heating to 60-70 ℃, stirring at the rotating speed of 70-100r/min for reaction for 20-25h, washing a product with ethanol, and performing vacuum drying at the temperature of 40-50 ℃ for 10-15h to obtain modified cellulose aerogel;
5) adding modified cellulose aerogel into a methanol solution, mixing and stirring to prepare a modified cellulose aerogel methanol dispersion solution, then adding talcum powder, oscillating and dispersing for 20-30min under 300-plus-500W ultrasonic wave, then performing centrifugal separation, washing, drying and airflow crushing to obtain modified cellulose aerogel powder taking the talcum powder as a carrier, and then mixing the powder with cleaned waste plastic, a catalyst and a foaming agent according to the proportion of 5-9%: 80-87%: 4-6%: 3 to 5 percent of the weight percent of the mixture is evenly mixed, and the plastic particles can be prepared by a double-screw extruder.
2. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 1), the mass fraction of the sulfuric acid solution is 63-70%; the mass volume ratio of the microcrystalline cellulose to the sulfuric acid solution is 1:10-15 g/ml; the concentration of the nano-cellulose suspension is 1-1.5 g/ml; the rotating speed of the stirring reaction is 50-80 r/min.
3. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 2), the volume ratio of the epichlorohydrin to the nano-cellulose suspension is 1: 9-12.
4. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 3), the mass ratio of the butyl methacrylate to the fluorooctyl ethyl methacrylate to the toluene to the benzoyl peroxide is 7-10:5-8:40-50: 0.2-0.5; the mass volume ratio of the reaction product to the ethanol solution is 1:30-40g/ml, and the mass fraction of the ethanol is 65-80%; the volume ratio of the tetrahydrofuran to the ethanol solution is 1: 15-20.
5. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 4), the mass ratio of the cellulose aerogel, the cuprous bromide, the methacrylic acid fluorine-containing copolymer and the mixed solution is 2-4:1:6-8: 20-30; the mass volume ratio of tetrahydrofuran, isopropanol and 2-vinylpyridine in the mixed solution is 13-17 ml: 4-6 ml: 1g of a compound; the mass ratio of the addition amount of the pentamethyl diethylenetriamine to the cellulose aerogel is 1: 2-2.5.
6. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 5), the preparation method of the catalyst is as follows: adding 10-15 parts of acetonitrile into a reactor, adding 2-3 parts of cerium trichloride and 1-2 parts of sodium iodide, stirring and mixing uniformly at the rotation speed of 150-200r/min, slowly adding 0.5-0.8 part of silica gel under the stirring state, continuously stirring for 20-30h at room temperature, then recovering the acetonitrile in the system by using a rotary evaporator, and drying the product for 6-8h at the temperature of 50-60 ℃.
7. The plastic particle for recycling the oil stain on the water surface as claimed in claim 1, wherein in the step 5), the mass fraction of the modified cellulose aerogel in the methanol dispersion liquid of the modified cellulose aerogel is 5-8%; the mass volume ratio of the talcum powder to the modified cellulose aerogel methanol dispersion liquid is 1:10-20 g/ml; the particle size of the modified cellulose aerogel powder taking the talcum powder as the carrier is 5-10 um; the foaming agent is any one of azo compounds, sulfonyl hydrazine compounds and nitroso compounds; the melting temperature of the double-screw extruder is 175-185 ℃; the waste plastic is at least one of recovered waste ABS plastic, waste PC plastic, waste PE plastic and waste HDPE plastic.
8. The plastic granules for the recovery treatment of the oil stain on the water surface according to any one of the claims 1 to 7, which is used by the following method: putting plastic particles on a water surface polluted by oil stains, recovering the plastic particles after the oil stains on the water surface are removed, putting the plastic particles into water containing hydrogen peroxide, adding a proper amount of nano zinc oxide, treating for 3-4h under 500-plus-600W microwave radiation, taking out the plastic particles, naturally airing, and then carrying out heat treatment for 3-4h in an oven at 60-70 ℃, wherein the content of the hydrogen peroxide in the water is 0.3-0.8%, and the adding amount of the nano zinc oxide is 1-2% of the total weight of the water body.
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| CN201911014867.1A CN110790973A (en) | 2019-10-24 | 2019-10-24 | Plastic particle for recycling water surface oil stains |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113618966A (en) * | 2021-08-30 | 2021-11-09 | 陕西师范大学 | Method for separating micro plastic and biochar |
| CN115109403A (en) * | 2022-08-08 | 2022-09-27 | 温州科尔新材料有限公司 | High-strength wear-resistant PC material and preparation process thereof |
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2019
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113618966A (en) * | 2021-08-30 | 2021-11-09 | 陕西师范大学 | Method for separating micro plastic and biochar |
| CN113618966B (en) * | 2021-08-30 | 2022-12-27 | 陕西师范大学 | Method for separating micro plastic and biochar |
| CN115109403A (en) * | 2022-08-08 | 2022-09-27 | 温州科尔新材料有限公司 | High-strength wear-resistant PC material and preparation process thereof |
| CN115109403B (en) * | 2022-08-08 | 2023-09-26 | 温州科尔新材料有限公司 | High-strength wear-resistant PC material and preparation process thereof |
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